Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
  • B01J13/20—After-treatment of capsule walls, e.g. hardening
  • B01J13/22—Coating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
  • B01J13/06—Making microcapsules or microballoons by phase separation
  • B01J13/14—Polymerisation; cross-linking
  • B01J13/18—In situ polymerisation with all reactants being present in the same phase
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3225—Polyamines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
  • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
  • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
  • C08G18/808—Monoamines
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
  • D06C7/00—Heating or cooling textile fabrics
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
  • D06M23/08—Processes in which the treating agent is applied in powder or granular form

Definitions

• the present invention relates to core-shell particles comprising a core which comprises at least one lipophilic compound and a shell which comprises at least one layer close to the core and one layer remote from the core.
• the invention further relates to the production of such core-shell particles and their use, in particular for finishing fibers and textiles.
• the microencapsulation of lipophilic compounds is well known: The mostly liquid or solid compounds are surrounded in the smallest portions with a shell and thus immobilized. The formation of the shell is usually generated by coacervation, interfacial reactions or in situ polymerization techniques.
• the compound to be encapsulated is usually dispersed in a liquid medium and the shell is formed at the interface between the compound and the medium. So far, special attention has been paid to melamine-formaldehyde microcapsules. As described above, a dispersion of medium and compound to be encapsulated is first produced, to which a melamine-formaldehyde prepolymer is added.
• the prepolymer hardens at the interface and forms a solid, impermeable shell with mechanically acceptable properties. Since formaldehyde is known to be released from the condensates, melamine-formaldehyde microcapsules are becoming less and less important for health reasons.
• EP 1 246 693 suggests adding melamine during the hardening phase of the melamine-formaldehyde resin shell in order to reduce the subsequent release of formaldehyde. From DE 2 242 910 it is known that a polyurea shell can be produced by an interface reaction of polyisocyanates with polyamines. EP 1 029 018 describes the formation of capsule walls by polymerizing acrylates. Attempts have been made to further functionalize the shell.
• No. 8,747,999 describes a core-shell particle, the shell of which is produced by simultaneous reaction of a melamine-formaldehyde resin with a diallyldimethylammonium chloride copolymer.
• the shell thus carries functional groups in the form of cationic units and reactive methylol functions.
• the shell cannot be functionalized to any degree, since this inevitably leads to a disturbance in the shell structure.
• EP 2 043 773 discloses the subsequent functionalization of a core-shell particle by coating with a polyelectrolyte.
• WO 2013/182855 discloses a core-shell particle with two polyurea shells arranged one above the other as a shell. The double encapsulation allows the permeability to be reduced.
• applying the second polyurea shell to the first polyurea shell is complicated and requires additional chemicals.
• No. 8,329,233 describes core shell particles which have a melamine-formaldehyde shell, which in turn is coated with a polyacrylate shell. The release of formaldehyde is to be prevented by the outer polyacrylate shell. The potential danger of
• Formaldehyde release cannot be excluded.
• EP 1 513 610 discloses a core-shell particle with a double wall structure with the aim of reducing the permeability.
• the sleeves made of polyurethane and polyurea are cross-linked, which can lead to defects in the respective sleeves.
• No. 7,025,912 describes a core-shell particle with a double-wall structure, the inner shell of which consists of polyurea and the outer shell of which is based on ethylenically unsaturated monomers.
• Polyurea shells are embedded in ethylenically unsaturated surfactants, which serve as anchor points for the second shell.
• the use of the surfactants can lead to disturbances, e.g. Pores or channels that come in the polyurea shell.
• the inner polyurea shell is not sufficiently compatible with the core material.
• the shell of the capsule should be inert to the lipophilic compound.
• the properties of the shell for example the permeability, mechanical strength, functionality, etc., should be variable and reproducible.
• functionality is understood in particular to mean the modification of the shell with functional, in particular functional chemical, groups.
• the aggregate state of the core can be gaseous, solid or liquid, the core is preferably solid at room temperature (20 ° C.) and can be in the form of a powder, for example. In another preferred embodiment, the core is liquid at room temperature (20 ° C.) and can also be in the form of a solution, emulsion or suspension at this temperature. In a preferred embodiment, the core comprises at least 80% by weight, more preferably at least 90 to 99% by weight, of the at least one lipophilic compound (based on the total mass of the core). In a preferred embodiment, the core consists of at least one lipophilic compound. In a preferred embodiment, the lipophilic compound has a water solubility of ⁇ 10 g / l, more preferably ⁇ 5 g / l, even more preferably ⁇ 3 g / l at 20 ° C.
• Preferred lipophilic compounds which can optionally be suspended in a carrier oil, are selected from pigments, dyes, fragrances, cosmetics, flame retardants, latent heat storage materials, biocides, catalysts, adhesives, adhesive components, hydrophobizing agents, polymer building blocks, isocyanates, oils, silicone oils, waxes or mixtures thereof.
• Suitable carrier oils are, for example, mono-, di- or triglyceride, mineral oil, silicone oil, castor oil and isopropyl myristate, or mixtures thereof.
• Latent heat storage materials refer to substances that have a phase transition.
• the phase transition should take place in the range of the respective application temperature; the latent heat storage material used is preferably a substance which has a solid / liquid phase transition in the temperature range from -20 to 120 ° C.
• Latent heat storage materials for clothing materials typically have a phase transition between 15 and 35 ° C.
• Suitable latent heat storage materials are preferably selected from ⁇ saturated or unsaturated, linear, branched, or cyclic hydrocarbon, preferably saturated or unsaturated, linear, branched, or cyclic Cio-C 4 o- hydrocarbon, more preferably linear or cyclic C 0 - C 40 alkane and aromatic C 6 -C 2 o hydrocarbon, most preferably n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, n-eicosane, cyclohexane, cyclooctane, cyclodecane, benzene, naphthalene, biphenyl,
• Ci-Cio-alkyl-ester preferably lauric, stearic, Oleic or behenic acid, lauryl, stearyl or oleyl alcohol, propyl palmitate, methyl stearate or methyl palmitate, and
• Dyes can be selected from reactive dyes such as Cl Reactive Red 2, disperse dyes such as Cl Disperse Yellow 42, acid dyes such as Cl Acid Blue 1, or basic dyes such as Cl Basic Violet 3 and mixtures thereof.
• Pigments are coloring substances that are practically insoluble in the application medium, e.g. oils.
• Preferred pigments are either inorganic or organic pigments. Pigments can also be classified according to their optical properties (specific color) and their technical properties (corrosion protection, magnetism). In the latter case, color pigments, magnetic pigments and mixtures thereof are preferred.
• Perfumes according to the present invention can be synthetic or natural in nature.
• Natural fragrances include e.g. oily flower and / or fruit bark extracts or essential oils.
• Synthetic fragrances include, for example, esters, ethers or aldehydes.
• the flame retardants used are preferably halogenated flame retardants, more preferably tetrabromobisphenol A (TBA), bromopolystyrene, chlorinated paraffins and dibromoneopentyl glycol (DBNPG), phosphate-containing flame retardants, more preferably organic
• Phosphoric acid esters or cyclic phosphate derivatives or mixtures thereof.
• Biocides according to the present invention are preferably selected from pesticides, fungicides, herbicides, insecticides, algicides, molluscicides,
• Acaricides rodenticides, bactericides, antibiotics, antiseptics, antibacterial, antiviral, antifungal, antiparasitic biocides and mixtures thereof.
• Cosmetics are preferably selected from anti-wrinkle agents, free radical scavengers, self-tanners and / or massage oils.
• Adhesives and adhesive components include, for example, one-component and two-component systems, for example based on lipophilic isocyanates, polyols, polyamines, carbodiimides, organotin compounds, acrylates and / or epoxides.
• Suitable oils preferably include natural or synthetic oils.
• Aliphates such as saturated, unsaturated and / or cyclic hydrocarbons, aromatic hydrocarbons, such as e.g. Benzene, xylene, naphthalene and / or toluene, vegetable oils such as e.g. Soybean oil, olive oil and / or rapeseed oil, silicone oils, and mixtures thereof.
• Suitable waxes include, for example, polyolefin waxes such as e.g. Polyethylene wax, carnauba wax, polyvinyl ether wax, and mixtures thereof.
• the shell comprises a layer close to the core and a layer remote from the core.
• the shell essentially consists of a layer close to the core and a layer remote from the core.
• the shell consists of a layer close to the core and a layer remote from the core and optionally auxiliaries.
• the layer remote from the core and / or the layer close to the core in particular the layer remote from the core and the layer close to the core, is covalently crosslinked.
• the layer close to the core directly surrounds the core.
• the layer remote from the core is arranged on the layer close to the core, ie between the layer remote from the core and In particular, no additional covalently cross-linked layer is arranged in the layer close to the core.
• the - possibly covalently cross-linked - layer close to the core and the - optionally covalently cross-linked - layer remote from the core are not covalently bonded to one another.
• the layer remote from the core and / or close to the core is / is preferably a polymer, in particular a crosslinked polymer, for example based on a polyolefin, polyacrylate, polyurethane, which may also contain one or more allophanate, carbodiimide, isocyanurate, biuret, uretdione -, Urea, iminooxadiazinedione and / or uretonimine groups can contain, polyallophanate, polycarbodiimide, polyisocyanurate, polybiurets, polyuretdione, polyurea, polyiminooxadiazinedione, polyuretonimine, epoxy resin, vinyl polymer, allyl polymer, in particular or based on a polyacrylate.
• a polymer in particular a crosslinked polymer, for example based on a polyolefin, polyacrylate, polyurethane, which may also contain one or more allophanate, car
• the layer close to the core is preferably based on a polymer of at least one ethylenically unsaturated monomer, in particular a crosslinked polyacrylate polymer.
• the core-distant layer is preferably based on a polyurethane, which may also contain one or more allophanate, carbodiimide, isocyanurate, biuret, uretdione, urea, iminooxadiazinedione and / or uretonimine groups, polyallophanate, polycarbodiimide, Polyisocyanurate, polybiurets, polyuretdione, polyurea, polyiminooxadiazinedione, and / or polyuretonimine, in particular based on a crosslinked polyurethane and polyurea.
• the layer close to the core is preferably inert to the core.
• the layer close to the core furthermore preferably contains no functional groups, in particular no functional groups which enable a covalent connection to the layer remote from the core.
• the near-core layer is obtainable by polymerizing at least one monomer with at least one ethylenically unsaturated group.
• the layer close to the core is particularly preferably obtainable by polymerizing at least one monomer with a monoethylenically unsaturated group and at least one monomer with a polyethylenically unsaturated group.
• Preferred ethylenically unsaturated groups are vinyl, vinyl ether, acrylic, CrC 6 alkyl acryl, allyl and / or allyl ether groups.
• Suitable monomers with at least one ethylenically unsaturated group preferably do not contain a nucleophilic group with an active hydrogen atom, in particular no nucleophilic group with an NCO-reactive hydrogen atom.
• the monomer having at least one ethylenically unsaturated group is preferably selected from compounds having the following structures:
• R 1 -CrC 6 -alkyl or -H, preferably -H or -CH 3 ,
• R 2 linear or branched Ci-C 24 alkyl
• R 3 linear or branched Ci-C2 4 alkylene
• R 7 polyester, especially obtainable by reaction of CrC 6 alkyldiols and C-
• Preferred monomers with an ethylenically unsaturated group are Cr C 24 alkyl esters of (meth) acrylic acid, CrC 24 vinyl ether, CrC 24 allyl ether and styrene.
• Alkyl in the sense of the present invention is a saturated, linear, cyclic or branched, hydrocarbon.
• Monomers with an ethylenically unsaturated group are particularly preferred methyl, ethyl, n-propyl, n-butyl, / so-butyl (sec-butyl and ferf-butyl) and / ' so-propyl (meth) acrylate.
• monomers with several, preferably 2, 3, 4 or 5, ethylenically unsaturated groups preference is given to using diesters of diols and (meth) acrylic acid and diallyl and divinyl ethers of these diols.
• Monomers with several ethylenically unsaturated groups are particularly preferred selected from ethanediol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol methacrylate, allyl acrylate, allyl methacrylate,
• Polyesters of polyols and (meth) acrylic acid and polyallyl and polyvinyl ethers of these polyols in particular butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and pentaeritrite tetra (meth) acrylate.
• the layer close to the core is preferably obtained by radical polymerization.
• suitable radical polymerization initiators are in particular peroxides, hydroperoxides, azo compounds, persulfates, perborates, or mixtures thereof.
• the layer close to the core is preferred by radical polymerization of methyl (meth) acrylate, ethyl (meth) acrylate, A / -propyl (meth) acrylate or N-butyl (meth) acrylate and butanediol di (meth) acrylate and / or
• Trimethylolpropane tri (meth) acrylate obtained.
• the molar ratio of monomers with one ethylenically unsaturated group to monomers with several ethylenically unsaturated groups is preferably 0 to 40, more preferably 2 to 40, even more preferably 4 to 30.
• the near-core layer can be obtained by polymerizing 100 mol% of monomers with an ethylenically unsaturated group.
• the polymer of the near-core layer preferably contains at least 55 mol%, more preferably at least 60 mol%, even more preferably at least 65 mol%, and most preferably at least 70 mol% of monomers with an ethylenically unsaturated group based on the total amount of the Monomers in the layer close to the core, for example 70 to 100 mol%.
• the proportion of monomers with several ethylenically unsaturated groups in the layer close to the core is, for example, 0 to 45 mol%, preferably up to 30 mol%, such as 5 to 30 mol%, more preferably up to 20 mol%, for example 10 to 20 mol %, more preferably up to 15 mol%, for example 10 to 15 mol% and most preferably 0.01 to 30 mol%, based on the total amount of monomers in the near-core layer.
• the near-core layer is obtainable by polymerizing at least 80 mol% of monomers with one ethylenically unsaturated group and up to 20 mol% of monomers with several ethylenically unsaturated groups.
• the ratio of monomers with one ethylenically unsaturated group and monomers with several ethylenically unsaturated groups is determined the degree of cross-linking.
• the degree of crosslinking has a decisive influence, for example, on the mechanical stability and permeability of the layer.
• the mechanical stability usually increases, and at the same time the permeability decreases.
• the thickness of the layer close to the core also plays a role in the mechanical stability and permeability. The thicker the layer, the lower the permeability and the higher the mechanical stability.
• the layer remote from the core preferably contains at least one urethane, allophanate, carbodiimide, isocyanurate, biuret, uretdione, urea, iminooxadiazinedione and / or uretonimine group, more preferably at least one urethane and / or urea group.
• the layer remote from the core is one
• the layer remote from the core is one
• the polyisocyanate is preferably aromatic, alicyclic or aliphatic.
• the polyisocyanate is preferably selected from methylene diphenyl isocyanate (MDI), polymeric MDI, tolylene diisocyanate (TDI), triphenylmethane-4,4 ', 4 “- triisocyanate, 2,4,6-triisocyanate toluene, isophorone diisocyanate (IPDI), 4,4'-methylene bis - (cyclohexyl isocyanate) (H12MDI), methyl 2,4-cyclohexane diisocynate, 1, 3,5-triisocyanate cyclohexane, 1, 3,5-trimethyl isocyanate cyclohexane, trimethylene diisocyanate, 1, 4,8-triisocyanatoctane, 1, 3, 6 Triisocyanate hexane, hexamethylene diisocyanate, xylene diisocyan
• NCO groups of the polyisocyanate can be blocked.
• the NCO groups are reacted with protective groups so that the isocyanate group does not react under normal storage conditions (for example 0 to 80 ° C.).
• the protective group can be split off, with the isocyanate groups regressing.
• the blocking of isocyanates is known to the person skilled in the art and is described in the literature (see DA Wieks, ZW Wieks Jr., Progress in Organic Coating 36 (1999), 148-172).
• Suitable blocking agents for isocyanates are, for example, malonic esters, such as, for example, dimethyl malonate, acetoacetate
• Bisulfite e.g. sodium bisulfite
• phenol e.g. 4-nitrophenol
• pyridinol e.g. 3-hydroxypyridine
• thiophenol e.g. 2-mercaptopyridine
• alcohol e.g. 2-ethy
• Imide e.g. succinimide
• imidazole amidine, guanidine, pyrazole (e.g. 3,5-dimethylpyrazole), triazoles (e.g. 1, 2,4-triazole) or amine (e.g. piperidine, tert-butylbenzylamine).
• amine e.g. piperidine, tert-butylbenzylamine.
• at least one catalyst can be added for the reaction of the isocyanate groups. All catalysts known to those skilled in the art which are used in polyurethane chemistry are suitable for this. For example, organic, in particular tertiary aliphatic, cycloaliphatic or aromatic amines, and Lewis acidic organic metal compounds come into consideration. This includes N, N'
• the catalyst is preferably used in amounts of 0.0001 to 10% by weight, particularly preferably in an amount of 0.001 to 5% by weight, based on the mass of the polyisocyanate.
• Pyrazole, oxime and benzylamine are preferably used to block isocyanate groups, more preferably 3,5-dimethylpyrazole, 2-butanone oxime and tert-butylbenzylamine.
• the deblocking temperature is in the range of 80 to 180 ° C, more preferably in the range of 120 to 160 ° C.
• An advantage of the reversible blocking reaction of isocyanate groups is the regeneration of a highly reactive functional group. For example, it is able to improve the connection of the core-shell particles to a substrate and thus also the abrasion and / or wash resistance.
• the compound, comprising at least two groups with an NCO-reactive hydrogen atom is preferably selected from polyol (including diol), polyester polyol, polyether polyol, polyurea, amino- and / or hydroxy-functionalized homo- or copolymer, polyamine (including diamine), hydroxy-functional amine, polyurethane and / or polycarboxylic acid.
• Polyether polyols are preferably based on C2-C5 alkylene oxide units, such as, for example, ethylene oxide, propylene oxide, butane oxide and / or pentane oxide units.
• Polyether polyols are preferably polyethylene glycol and / or polypropylene glycol.
• Polyester polyols are preferably reaction products of diols (e.g. 1,4-butanediol, diethylene glycol, or 1,6-hexanediol) with dicarboxylic acids (e.g. glutaric acid, adipic acid or pimelic acid), and / or lactones (e.g. e-caprolactone).
• diols e.g. 1,4-butanediol, diethylene glycol, or 1,6-hexanediol
• dicarboxylic acids e.g. glutaric acid, adipic acid or pimelic acid
• lactones e.g. e-caprolactone
• Hydroxy-functionalized polymers are preferably based on hydroxy-functional vinyl monomers e.g. 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
• Suitable polyamines have at least two primary and / or secondary amines. Polyvinylamine, diethylene triamine, pentaethylene hexamine, toluenediamine, piperazine, polyethyleneimine and mixtures thereof are preferably used.
• Preferred hydroxy-functional amines are ethanolamine or aminopropyl alcohol.
• the compound comprising at least two groups with an NCO-reactive hydrogen atom is preferably water-soluble (> 10 g / l at 20 ° C.).
• Preferred is the molar ratio of NCO groups to groups with NCO reactive hydrogen, e.g. -OH, -NH2, -NHR, between 1 and 100, preferably 2 and 100, more preferably 5 and 100 and even more preferably 5 and 80.
• the addition product of the layer remote from the core comprises about 1 to 50 mol%, more preferably about 3 to 40 mol% and even more preferably about 5 to 20 mol% of the compound, comprising at least two groups with NCO-reactive hydrogen atom, based on the amount of substance of the free isocyanate groups originally available.
• the layer remote from the core contains at least 1 mol%, preferably at least 2.5 mol%, even more preferably at least 5 mol%, of polyols and / or polyamines, based on the amount of substance of the free isocyanate originally available -Groups.
• the addition product of the layer remote from the core preferably comprises about 40 to 99% by weight of polyisocyanate, more preferably 60 to 99% by weight, even more preferably 70 to 99% by weight, even more preferably 80 to 99% by weight and am most preferably about 90 to 99% by weight of polyisocyanate based on the total mass of the layer remote from the core.
• the layer remote from the core has at least one additional functional group, preferably an anionic, cationic or nonionic group or an ethylenically unsaturated group (for example vinyl, allyl or (meth) acrylic group).
• the at least one additional functional group in particular an anionic, cationic or nonionic group, brings about improved dispersibility and dispersion stability of the core-shell particles in an aqueous environment.
• Core-shell particles with ethylenically unsaturated groups in the layer remote from the core can be polymerized or crosslinked by thermal treatment or treatment with energetic radiation.
• the anionic group preferably comprises at least one carboxylate, phosphate, phosphonate, sulfate, sulfonate group.
• the anionic group more preferably comprises the formula (I)
• X is S0 3 , S0 4 , COO, P0 4 2 or P0 3 2 , in particular S0 3 or COO, and
• L is linear or branched, saturated or unsaturated C1-C10 alkylene, which is optionally substituted by -OH.
• the functional anionic group can be introduced into the layer remote from the core by reaction of an isocyanate group of the polyisocyanate with a compound which, in addition to an anionic group, has an isocyanate-reactive hydrogen atom become.
• the compounds mentioned above preferably have the formula ALX, where L and X are as defined above and A is preferably OH, NH 2 or NHR.
• the functional cationic group is a quaternary ammonium ion or an ammonium salt and more preferably has formula (II):
• Y is NHR 8 R 9 + or NR 8 R 9 RIO + , R 8 , Rg and Rio are each independently H or linear or branched, saturated or unsaturated, Ci-Cio-alkyl, which is optionally substituted with -OH and / or -COOH and
• the cationic functional group is preferably introduced via a compound which, in addition to an isocyanate-reactive hydrogen atom, has a quaternary ammonium ion, secondary or tertiary amine.
• Preferred compounds are N-methyldiethanolamine and A /, A / -dimethylethanolamine.
• the amines can then be converted into quaternary ammonium groups or ammonium ions by alkylation or protonation.
• the amines are preferably methylated. Suitable methods for alkylation and corresponding alkylating agents are known to the person skilled in the art.
• Preferred alkylating agents are dimethyl sulfate, methyl chloride, or methyl tosylate.
• Preferred nonionic functional groups include polyalkylene oxides, preferably polyethylene oxide and / or polypropylene oxide.
• Preferred polyalkylene oxides are methyl-capped-polyethylene glycol (MPEG), methyl-capped-polypropylene glycol or methyl-capped-poly- (ethylene glycol / propylene glycol).
• the functional nonionic group can be reacted by reacting an isocyanate group of the polyisocyanate with a compound which has an isocyanate-reactive hydrogen atom in addition to a nonionic group the far core layer are introduced.
• the functional ethylenically unsaturated group can be obtained by reacting an isocyanate group of the polyisocyanate with a compound which, in addition to at least one ethylenically unsaturated group, has an isocyanate-reactive hydrogen atom, be introduced into the layer remote from the core.
• Compounds which have an isocyanate-reactive hydrogen atom in addition to at least one ethylenically unsaturated group are preferred (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, allylamine, acrylamide,
• the additional functional group is covalently bound to the layer remote from the core via a urethane group.
• an addition product composed of at least one polyisocyanate and at least one compound comprising at least two groups with an NCO-reactive hydrogen atom in the layer remote from the core up to 50%, more preferably 5-40%, even more preferably 10 to 30% of those originally available NCO groups in the polyisocyanate can be reacted with a compound comprising at least one functional group.
• an addition product composed of at least one polyisocyanate and at least one compound comprising at least two groups with an NCO-reactive hydrogen atom in the layer remote from the core up to 30%, more preferably up to 20%, even more preferably 0.1 to 20% of the originally Available NCO groups in the polyisocyanate can be reacted with a compound comprising at least one functional group.
• the layer remote from the core and the layer close to the core can optionally be covalently bonded to one another.
• the layer close to the core and away from the core are preferably not covalently bonded to one another.
• Surface-active reagent in particular surfactant, defoamer, protective colloid or thickener, may be arranged between the layer remote from the core and the layer close to the core.
• the compounds, which can be arranged mainly between the layer remote from the core and the layer close to the core make up, for example, 0 to 70% by weight, preferably 5 to 30% by weight, more preferably 10 to 15% by weight, based on the total mass of the core away and the near-core layer.
• the core-shell particle according to the invention comprises
• the core-shell particle consists of
• auxiliary in particular surface-active reagent, preferably surfactant, binder, defoamer, protective colloid or thickener.
• the core-shell particle consists of
• the core-shell particle according to the invention comprises
• the layer close to the core being obtainable by polymerizing at least one monomer having at least one ethylenically unsaturated group.
• the core-shell particle according to the invention comprises
• the near-core layer is obtainable by polymerizing at least one monomer having at least one ethylenically unsaturated group and the distant-core layer contains at least one urethane, allophanate, carbodiimide, isocyanurate, biuret, uretdione, urea, iminooxadiazinedione or uretonimine group and is preferably a polyurethane.
• the weight ratio between the near-core layer and the remote core layer is preferably 50:50 to 95: 5% by weight, more preferably 70:30 to 90:10% by weight and most preferably 80:20 to 90:10% by weight. % based on the total mass of the near-core and the far-away layer.
• the weight ratio of core: shell is preferably in the range from 50:50 to 95: 5, preferably 70:30 to 90:10.
• the layer remote from the core is preferably permeable to the lipophilic compound.
• Methods for determining the permeability of the core-shell particles are known. The permeability can be determined, for example, via the loss of latent heat by means of dynamic differential scanning calorimetry (DSC) (cf. also examples).
• the core-shell particles according to the invention are preferably spherical or ellipsoidal, more preferably spherical.
• the mean diameter (D50) of the core-shell particles according to the invention is preferably 0.1 to 100 pm, more preferably 0.5 to 80 pm and even more preferably 1 to 75 pm (e.g. determined by laser diffraction).
• Another aspect of the invention relates to a composition comprising at least one core-shell particle according to the invention.
• the composition preferably also contains water.
• the composition further contains at least one auxiliary, preferably at least one surface-active reagent, in particular a surfactant, a binder, a defoamer, a protective colloid and / or a thickener.
• at least one auxiliary preferably at least one surface-active reagent, in particular a surfactant, a binder, a defoamer, a protective colloid and / or a thickener.
• Nonionic, anionic or cationic surfactants and / or mixtures thereof can be used in particular as surface-active reagents.
• Preferred nonionic surfactants are e.g. Alkoxylation products of fatty acids, fatty acid esters, fatty acid amides, aliphatic alcohols and sugar derivatives. Ethoxylation products of linear or branched aliphatic alcohols having 6 to 22 carbon atoms are preferably used.
• Preferred cationic surfactants are quaternary ammonium salts, such as, for example, di- (C10-C24) -alkyldimethylammonium chloride, (C10-C24) -alkyldimethylethylammonium chloride or -bromide, (C10-C24) -alkyltrimethylammonium chloride or -bromide, (C10-C24dimoniumchloride) alkylbenzylammonium chloride .
• quaternary ammonium salts such as, for example, di- (C10-C24) -alkyldimethylammonium chloride, (C10-C24) -alkyldimethylethylammonium chloride or -bromide, (C10-C24) -alkyltrimethylammonium chloride or -bromide, (C10-C24dimoniumchloride) alkylbenzylammonium chloride
• Anionic surfactants are especially fatty alcohol sulfates such as Sodium lauryl sulfate, alkyl sulfonates such as e.g. Sodium lauryl sulfonate, alkylbenzenesulfonate, e.g. Sodium dodecylbenzenesulfonate and fatty acid salts such as e.g. Sodium stearate and phosphate esters, e.g. Phosphate esters of aliphatic alcohols.
• fatty alcohol sulfates such as Sodium lauryl sulfate, alkyl sulfonates such as e.g. Sodium lauryl sulfonate, alkylbenzenesulfonate, e.g. Sodium dodecylbenzenesulfonate and fatty acid salts such as e.g. Sodium stearate and phosphate esters, e.g. Phosphate
• the surface-active reagents are preferably added in an amount of 0-10% by weight, more preferably 0 to 5% by weight, even more preferably 0 to 2% by weight, based on the mass of the total composition.
• Preferred protective colloids are preferably water-soluble polymers, for example polyvinyl alcohol, cellulose derivatives, in particular hydroxyalkyl cellulose or carboxyalkyl cellulose, gum arabic, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone and / or maleic anhydride copolymers, polyvinyl alcohol is particularly preferred.
• the protective colloid is preferably present in amounts of 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.5 to 5% by weight, based on the mass of the total composition.
• Preferred binders are polymers with a glass transition temperature in the range from -45 to +45 ° C., particularly selected from polymers based on (meth) acrylic acid ester, styrene, isoprene, butadiene, vinyl acetate and / or isocyanate.
• the binder is preferably in amounts of 0.01 to 20% by weight, more preferably 0.01 to 5% by weight, based on the mass of the
• Preferred defoamers are selected from mineral oil, silicic acid, silicone-containing compounds, such as e.g. Organosilicon compounds.
• the defoamer is preferably present in amounts of 0.01 to 10% by weight, more preferably 0.01 to 2% by weight, based on the mass of the total composition.
• composition according to the invention preferably comprises 10 to 55% by weight, more preferably 15 to 45% by weight, even more preferably 20 to
• Another aspect of the present invention is a method for producing the core-shell particle or the composition according to the invention.
• the process includes the steps:
• step (i) is preferably carried out at temperatures above room temperature, particularly preferably at temperatures above the melting point of the lipophilic compound (s).
• an emulsion can form, in particular an oil-in-water emulsion, in which the water forms the continuous phase and the lipophilic compound (s) together with at least part of the monomer forms the disperse phase.
• the protective colloid stabilizes the emulsion.
• the stabilization of the emulsion can be further improved by adding surface-active reagents become.
• Protective colloids and surface-active reagents are as defined above and are preferably used in the corresponding amounts.
• Preferred polymerization initiators are radical initiators, in particular a peroxide, an azo compound, a persulfate
• the decomposition temperature of the polymerization initiators is preferably above the melting point of the lipophilic compound, in particular up to 50 ° C. above the melting point of the lipophilic compound.
• Suitable initiators are azo compounds, such as, for example, 2,2'-azobis- (2-amidinopropane) dihydrochloride, 2,2'-azobis- (A /, A / -dimethylene) isobutyramidine-dihydrochloride, 2- (carbamoylazo) isobutyronitrile, 4 , 4'-azobis (4-cyanovaleric acid), 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, and 2,2 , -azobis (2,4-dimethylvaleronitrile).
• 2,2'-azobis- (2-amidinopropane) dihydrochloride 2,2'-azobis- (A /, A / -dimethylene) isobutyramidine-dihydrochloride, 2- (carbamoylazo) isobutyronitrile, 4 , 4'-azobis (4-cyanovaleric acid), 2,2'-azobis
• Suitable peroxide compounds are, for example, acetylacetone peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perneohexanoate, tert-butyl perisobutyrate, tert-butyl per-2-ethylhexanoate, tert-butyl peranoate .-Butyl permaleate, tert-butyl perbenzoate, tert-butyl per-3,5,5-trimethylhexanoate and tert-amyl perneodecanoate, and
• Particularly preferred initiators are 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride and 2,2'-azobis (2,4-dimethylvaleronitrile), whose 10-hour half-life in the temperature range from 30 to 100 ° C.
• the initiator can be used as a solid or solution.
• the polymerization initiators are usually used in amounts of 0.01 to 5% by weight, preferably 0.1 to 3.5% by weight, based on the total mass of the monomers having at least one ethylenically unsaturated group.
• the chain length of the polymers obtainable from monomers with at least one ethylenically unsaturated group can be controlled via chain regulators. Such chain regulators are known to the person skilled in the art.
• Preferred chain regulators are sulfur-containing compounds, in particular thiols, in particular lauryl mercaptan or ethylhexyl thioglycolate.
• the chain regulator is typically used in amounts of 0 to 4% by weight, more preferably 0.01 to 3% by weight, based on the total mass of the monomers with at least one ethylenically unsaturated group.
• the mixture is further emulsified under shear forces, in particular using a homogenizer, for example Ultra-Turrax® or Dispax®.
• the average droplet size (D50) of the disperse phase determined by means of light radiation is preferably from 0.1 to 100 pm, more preferably 0.5 to 80 pm, even more preferably 1 to 75 pm.
• step (iii) The emulsion obtained in step (ii) is then treated in step (iii) at elevated temperature, preferably at 25 to 100 ° C, more preferably at 50 to 100 ° C, with stirring.
• Treatment step (iii) usually lasts 0.5 to 8 hours, preferably 1 to 8 hours, more preferably 3 to 4 hours.
• 90 to 100% of the monomers are preferably reacted with at least one ethylenically unsaturated group.
• Step (ii) and step (iii) are preferably carried out under a protective gas atmosphere, in particular under nitrogen or argon.
• the radical polymerization causes a polymer to form in situ at the interface between the disperse phase and the continuous phase. This preferably results in spherical or ellipsoidal particles from cores which are surrounded by the layer close to the core.
• the particles so obtained have preferably a diameter D50 of 0.1 to 100 miti, preferably 0.5 to 80 mhh, more preferably 1 to 75 miti.
• step (iv) at least one - optionally partially blocked - polyisocyanate and at least one compound comprising at least two groups having an NCO-reactive hydrogen atom are added to the particles from step (iii) dispersed in the continuous phase. If appropriate, at least one compound comprising at least one functional group and an NCO-reactive hydrogen atom is added in this step. The latter compound is added in particular if a functional layer remote from the core is to be obtained. Alternatively, the polyisocyanate may already contain at least one functional group. Step (iv) usually takes place at temperatures of 25 to 100 ° C., preferably 50 to 100 ° C.
• step (iv) the optionally partially blocked polyisocyanate orients itself to the layer close to the core surrounding the core. Subsequent addition of the compound comprising at least two groups with an NCO-reactive hydrogen atom forms a layer remote from the core on the layer close to the core.
• step (v) the mixture obtained in step (iv) is optionally thermally treated at elevated temperature.
• Step (v) - if carried out - is preferably carried out at temperatures from 25 to 100 ° C., preferably 30 to 90 ° C.
• the reaction time is preferably 0.25 to 4 hours.
• Conditions are preferably 90 to 100%, more preferably 95 to 100% of all NCO groups implemented.
• auxiliaries such as binders, defoamers, surface-active reagents and / or thickeners can optionally be added.
• a composition according to the invention comprising the core-shell particles according to the invention and water is obtained.
• the composition obtained forms a stable dispersion.
• the core-shell particles therein have a diameter D50 of 0.1 to 100 miti, preferably 0.5 to 80 miti, more preferably 1 to 75 miti.
• step (vi) it may be possible to equalize the particle size distribution via filtration steps.
• the core-shell particles can optionally be isolated in step (vii) by the processes known to the person skilled in the art by at least partially removing the water. Preferred processes are centrifugation, filtration, distillation and / or spray drying. Isolated core-shell particles can, for example, be incorporated into a preparation as a slurry or powder. In another aspect, the present invention is directed to core-shell particles obtainable by the method described above.
• the core-shell particles and compositions of the invention can be used in a variety of technical fields. For example, they can be used to functionalize fabrics, in particular fibers, textile fabrics, paints, varnishes, building materials, Plastics and / or plastic foams are used.
• One aspect of the present invention is therefore the use of the core-shell particles according to the invention or the composition according to the invention for the functionalization of flat structures, in particular fibers, textile flat fabrics, building materials, plastics or plastic foams, for example polyurethane, polystyrene, latex and melamine resin foams, Paints and varnishes.
• Textiles are to be understood in particular as fibers or textile fabrics, such as textile fabrics, nonwovens (for example nonwovens or filters).
• the core-shell particles can be added to a melt or in the form of an aqueous dispersion of the fiber matrix and used in a spinning process, for example in a melt spinning process or a wet spinning process.
• Fibers mean natural fibers as well as synthetic fibers. "Natural fibers” preferably contain cotton, wool and / or silk. “Synthetic fibers” or “synthetic fibers” are produced synthetically from natural and / or synthetic polymers and preferably contain polyester, polyolefin, for example preferably polyethylene or polypropylene, more preferably polypropylene, polyamide, polyaramide, such as Kevlar® and Nomex®, polyacrylonitrile, Spandex and / or viscose. Textiles are to be understood in particular as fibers or textile fabrics. A “textile” is made of several fibers and is preferably linear or flat.
• Line-shaped textile is understood to mean, for example, a yarn, a thread or a rope.
• Fiber textiles are preferably nonwovens, felts, fabrics, knitted fabrics and braids. Textiles can contain natural fibers and synthetic fibers or mixtures thereof. Another object of the present invention is a method for finishing fabrics, in particular textiles, comprising the steps
• step (c) thermal treatment of the fabric.
• an aqueous composition is usually prepared in the desired concentration. The concentration of the composition is chosen so that the desired order results in each case.
• Further preparation agents can be added to the composition. Additional preparation agents include chemicals for crease-free finishing (e.g. methylol compounds from
• Dihydroxyethylene urea or methylol melamine ether with different degrees of methylolation Dihydroxyethylene urea or methylol melamine ether with different degrees of methylolation), flame retardants or softeners.
• the composition is applied to the fabric, in particular the textile fabric, using conventional methods known to those skilled in the art, for example by forced application, exhaust process, spraying, impregnation, splashing, printing, coating, for example by transfer coating or rotary printing, or padding.
• the composition according to the invention is applied to the foulard by soaking the fabric and then squeezing it off.
• the drying and thermal treatment of the fabric obtained in step (b) is preferably carried out in step (c) at temperatures between 130 to 170 ° C.
• the treatment is preferably carried out in the stenter dryer. At the specified temperatures, the blocking groups, if present, also split off and evaporate.
• the resulting reactive isocyanate group reacts with isocyanate-reactive hydrogen atoms of the fabric and / or the other components, so that the core-shell particles are covalently bound to the fabric.
• the thermal treatment of the fabric is preferably carried out in 0.5 to 10 minutes, particularly preferably in 1 to 5 minutes. The duration of the thermal treatment also depends on the temperatures used.
• the present invention therefore also relates to fabrics, in particular fibers or textile fabrics comprising the core-shell particles according to the invention or the composition according to the invention.
• the core-shell particles or the composition according to the present invention can also be used in building materials, for fixing polymeric moldings and / or in polymeric coating compositions.
• the core-shell particles according to the invention are preferably used as a functional additive in mineral coating compositions such as plaster or in wall paints.
• the core-shell particles according to the invention are particularly suitable for the functionalization of polymer moldings and polymeric coating compositions made of thermoplastic and thermosetting plastics, the core-shell particles of which are not destroyed during processing.
• thermoplastic and thermosetting plastics are epoxy resins, urea resins,
• the core-shell particles according to the invention can be functionalized easily and variably without the primary properties of the core-shell particles, such as e.g. To influence permeability and mechanical stability.
• the permeability and mechanical stability of the particles are variably adjusted via the layer close to the core.
• the layer close to the core is preferably made of a material that is inert to the core.
• the layer remote from the core can be variably functionalized.
• the non-core layer does not influence the property profile of the near-core layer.
• the core-shell particles according to the invention and the method according to the invention also enable a modular system in which the cores coated with the layer close to the core are provided in stock and can then be modified as desired with different functional groups via the layer remote from the core without the Change the properties of the core (primary particle) surrounded by the layer close to the core.
• Aqueous initiator :
• Aqueous initiator :
• Aqueous initiator :
• Example 2 The sample was produced analogously to Example 1. A dispersion with a solids content of approximately 36% was obtained.
• the permeability of the core-shell particles was determined via the loss of latent heat by means of dynamic differential calorimetry (English differential scanning calorimetry - DSC). For this purpose, a latent heat storage material was wrapped and the dispersion was diluted on a textile fabric.
• Part of the textile was dried at 20 ° C for 24 h, while another part was dried at 150 ° C for 3 min.
• the difference in the measured enthalpy of fusion between air-dried and heat-dried sample gives the tightness.
• this DSC method was carried out for the same sample at different times in the process. For example, the permeability was determined after the formation of the polyacrylate layer close to the core and then again after the polyurethane layer remote from the core had been put on.
• the core remote layer is primarily responsible for the functionalization.
• Exemplary embodiment - 4 Exemplary embodiment 4 - as described in exemplary embodiment 1 - was carried out, the partially blocked isocyanate being varied as follows.
• Exemplary embodiment 5 was carried out as described in exemplary embodiment 1, the oil phase being premixed without an acrylate crosslinker.
• the exact composition is given in Table 1. Sufficient tightness of the layer close to the core cannot be guaranteed without acrylate crosslinker.
• Exemplary embodiment 6 was carried out as described in exemplary embodiment 1, the partially blocked isocyanate being varied as follows. Functionalization with radiation-crosslinkable groups
• the polyisocyanate was added dropwise to this suspension and stirred in.
• the polyamine was then added dropwise and the temperature increased to 80 ° C.
• the dispersion was cooled to room temperature, mixed with emulsifiers, defoamers and thickeners and adjusted to pH 8.5 with sodium hydroxide solution.
• aqueous solution of the aqueous initiator was added to the resulting dispersion under protective gas and the mixture was stirred again for 60 minutes. After this time, the dispersion was cooled to room temperature, mixed with emulsifiers, defoamers and thickeners and adjusted to pH 8.5 with sodium hydroxide solution.
• Table 2 Type of functionalization and permeability of the core-shell particles according to the invention and the comparison particles
• a shell comprising at least one layer close to the core and one layer remote from the core.
• Core-shell particles according to item 1 the layer remote from the core being arranged on the layer close to the core.
• Core-shell particles according to item 1 or 2 the layer close to the core surrounding the core.
• Core-shell particles according to one of the preceding points, the core being solid at room temperature (20 ° C.).
• Core-shell particles according to one of the items 1-3 the core being liquid at room temperature (20 ° C.), preferably in the form of a solution, emulsion or suspension, or solid, preferably in the form of a powder.
• the lipophilic compound having a water solubility of ⁇ 10 g / l, preferably ⁇ 5 g / l, more preferably ⁇ 3 g / l at 20 ° C.
• the lipophilic compound being selected from pigments, dyes,
• Latent heat storage materials biocides, catalysts, adhesives, adhesive components, water repellents, polymer building blocks, isocyanates, oils, silicone oils, waxes or mixtures thereof.
• the latent heat storage material being selected from
• Hydrocarbon more preferably linear or cyclic Ci 0 - C 4 o-alkane and aromatic C6-C20 hydrocarbon, most preferably n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, n-eicosane, cyclohexane, cyclooctane, cyclodecane , Benzene, naphthalene, biphenyl,
• Ci-Cio-alkyl ester preferably lauric, stearic , Oleic or behenic acid, lauryl, stearyl or oleyl alcohol, propyl palmitate, methyl stearate or methyl palmitate, and
• Core-shell particles according to item 7 the dye being selected from reactive dye, such as e.g. C.I. Reactive Red 2, disperse dye, e.g. C.I. Disperse Yellow 42, acid dye, such as e.g. C.I. Acid Blue 1, or basic dye, e.g. C.I. Basic Violet 3, and mixtures thereof.
• the pigments being selected from organic or inorganic pigments, in particular color pigments, magnetic pigments, and mixtures thereof.
• Core-shell particles according to item 7 the fragrances being selected from synthetic or natural fragrances.
• the flame retardants being halogenated flame retardants, preferably tetrabromobisphenol A (TBA), bromopolystyrene, chlorinated paraffins and dibromoneopentylglycol (DBNPG), phosphate-containing flame retardants, preferably organic phosphoric acid esters or cyclic phosphate derivatives, or mixtures thereof.
• the biocides being selected from pesticides, fungicides, herbicides, insecticides, algicides, molluscicides, acaricides, rodenticides, bactericides, antibiotics,
• Core-shell particles according to item 7 the cosmetics being selected from anti-wrinkle agents, free radical scavengers, self-tanning agents and massage oils.
• Core-shell particles according to one of the preceding points, the layer close to the core being obtainable by polymerizing at least one monomer having at least one ethylenically unsaturated group.
• Core-shell particles according to item 15 wherein the monomer with at least one ethylenically unsaturated group has no nucleophilic group with an active hydrogen atom, in particular no NCO-reactive hydrogen.
• Core-shell particles according to item 15 or 16 the layer close to the core being obtainable by radical polymerization.
• R 1 -CrC 6 -alkyl or -H, preferably -H or -CH 3 ,
• R 2 linear or branched CrC 24 alkyl
• R 3 linear or branched CrC 24 alkylene
• R 7 polyester, in particular obtainable by reaction of C1-C6 alkyl diols and Ci-C 6 alkyldicarboxylic acids, such as diesters, eg malonic, Oxal Textreester, BernsteinTexreester, glutarate or adipate and
• n 0-20 core-shell particles according to one of the items 15-19, the molar ratio of monomers with one ethylenically unsaturated group to monomers with several ethylenically unsaturated groups being 2 to 40, preferably 4 to 30.
• the layer remote from the core being an addition product of at least one polyisocyanate and at least one compound comprising at least two groups having an NCO-reactive hydrogen atom, preferably hydroxy,
• polyisocyanate is aromatic, alicyclic or aliphatic preferably selected from methylene diphenyl isocyanate (MDI), polymeric MDI, tolylene diisocyanate (TDI), triphenylmethane-4,4,, "-triisocyanate 4, 2 , 4,6-triisocyanatetoluene,
• MDI methylene diphenyl isocyanate
• TDI tolylene diisocyanate
• triphenylmethane-4,4 triphenylmethane-4,4,, "-triisocyanate 4, 2 , 4,6-triisocyanatetoluene
• IPDI Isophorone diisocyanate
• H12MDI 4,4'-methylenebis (cyclohexyl isocyanate)
• methyl 2,4-cyclohexane diisocyanate 1, 3,5-
• Triisocyanate cyclohexane 1, 3,5-trimethyl isocyanate cyclohexane
• Core-shell particles according to item 23 0.1 to 80%, preferably 1 to 50%, more preferably 1 to 30% of the NCO groups of the polyisocyanate being blocked. 26. Core-shell particles according to one of the items 22-25, the
• Compound comprising at least two groups with an NCO-reactive hydrogen atom is selected from polyols, polyester polyols, polyether polyols, polyureas, amino- and / or hydroxy-functionalized homo- or copolymers, polyamines and hydroxy-functional amines.
• Core-shell particles according to one of the items 22-26 the molar ratio of NCO groups to groups having an NCO-reactive hydrogen atom between 1 and 100, preferably 2 and 100, more preferably 5 and 100 and even more preferably 5 and 80 lies.
• the layer remote from the core having at least one functional group, preferably an anionic, cationic or non-ionic group.
• the anionic group comprising at least one carboxylate, phosphate, phosphonate, sulfate or sulfonate group and preferably having the formula (I):
• X is S0 3 , S0 4 , COO, P0 4 2 or P0 3 2 , and
• L is linear or branched, saturated or unsaturated C1-C-10 alkylene, which is optionally substituted with -OH.
• Core-shell particles according to item 28 wherein the cationic functional group comprises at least one quaternary ammonium ion or an ammonium salt and preferably has the formula (II): -L-Y
• Y is NHR 8 Rg + or NR 8 RgRio + ,
• R 8 , Rg and R 10 are each independently H or linear or branched, saturated or unsaturated, C1-C1 o-alkyl, which is optionally substituted by OH and / or COOH and
• Core-shell particles according to item 28 the nonionic functional group being a polyalkylene oxide, preferably polyethylene oxide and / or
• Core-shell particles according to one of the items 28-31 the functional group being bound to the layer remote from the core via a urethane group.
• Core-shell particles according to one of items 27-31 wherein 0-30%, preferably 0 to 20%, more preferably 0.1 to 20%, of the NCO groups in the polyisocyanate are reacted with a compound comprising at least one functional group , Composition comprising at least one core-shell particle according to one of items 1-33.
• Composition according to item 34 the composition comprising water.
• composition according to item 34 or 35 wherein the composition further contains at least one surface-active reagent, in particular surfactant, a binder, a defoamer, a protective colloid and / or a thickener.
• the binder is a polymer with a glass transition temperature in the range from -45 to +45 ° C, in particular a polymer based on (meth) acrylic acid ester, styrene, isoprene, butadiene, vinyl acetate, and / or isocyanate.
• the binder is a polymer with a glass transition temperature in the range from -45 to +45 ° C, in particular a polymer based on (meth) acrylic acid ester, styrene, isoprene, butadiene, vinyl acetate, and / or isocyanate.
• Defoamer is a mineral oil, a silica or a silicone-containing defoamer.
• the disperse phase has a diameter D 50 of 0.1 to 100 ⁇ m, preferably 0.5 to 80 ⁇ m and more preferably 1 to 75 ⁇ m.
• the protective colloid being selected from water-soluble polymer, in particular polyvinyl alcohol, cellulose derivatives, in particular hydroxyalkyl cellulose or carboxyalkyl cellulose, gum arabic, polyacrylic acid, polyacrylamides, polyvinylpyrrolidone and / or maleic anhydride copolymers.
• the polymerization initiator is a radical initiator, in particular a peroxide, an azo compound, a persulfate, a hydroperoxide and / or a redox initiator, or mixtures thereof.
• step (v) is preferably carried out for 0.25 to 4 hours, preferably at temperatures from 25 to 100 ° C., preferably 30 to 90 ° C. 50.
• Core-shell particles obtainable by a process according to the
• core-shell particles according to one of items 1-33 or 50 or the composition according to one of items 34-39 for the functionalization of fabrics, in particular fibers, textile fabrics, building materials, plastics or plastic foams, paints and varnishes.
• a method for finishing fabrics, in particular textiles, comprising the steps

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